As is well-known, it is a great challenge that the smooth TiO2 nanospheres are coated by MoS2 nanosheets to form the core-shell nanostructure owing to their poor interaction. Herein, we report 3D black N-TiO2-x@MoS2 core-shell nanostructures synthesized by a mild and effective strategy combined with a typical hydrothermal reaction and an in situ solid-state chemical reduction method followed by 350 degrees C calcination under an argon atmosphere. The prepared samples are characterized in detail by X-ray diffraction, Raman, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The results suggest that the 3D N-TiO2-x@MoS2 photocatalyst is successfully doped with N and Ti3+, and simultaneously coupling with MoS2 to form the core-shell heterojunction nanostructure. The N and Ti3+ co-doped and hybrid heterostructures can effectively utilize visible-light and solar energy to degrade methyl orange and produce hydrogen. The degradation rate of methyl orange and the hydrogen production rate are as high as 91.8% and 1.882 mmol h(-1) g(-1). To the best of our knowledge, this work is the first instance of combining MoS2 with N and Ti3+ co-doped TiO2, and the proposed photocatalytic mechanism will provide a new perspective for high activity photocatalyst in future. (C) 2016 Elsevier B.V. All rights reserved.